Lubricant



Patented Sept. 10, 1940 LUBRICANT Bert H. Lincoln, Ponca City, Okla.,and Alfred Henriksen, deceased, late of Ponca City, Okla, by John W.Wolfe, administrator de bonis non, Ponca City, Okla, assignors, by mesneassignments, to The Lnbri-Zol Development Corporation, Cleveland, Ohio,a corporation of Delaware I No Drawing. Application September 16, 1938,

I SerialNo. 230,339

17 Claims. (01.252-48) Our invention relates to lubricating oils andparticularly to an oil having high pressure-sustaining film-formingqualities.

" N This application is a continuation in part of copending applicationSerial No. 687,682, filed August 31, 1933.

Hydrocarbon lubricating oils per se will not withstand high pressuresimposed during thin film or non-viscous lubrication. Under pressure thefilm of oil will rupture. A metal to metal contact under comparativelylow loads results. This weakness, inherent in the very best qualityhydrocarbon lubricants, has prevented designers of mechanical equipmentfrom making certain desirable changes which would greatly improvemechanical devices in general.

One object of our invention isto increase the load-carrying propertiesof hydrocarbon lubricants by imparting to them an increased filmstrength. Another object of this invention is to obtain such increasedfilm strength without at the same time rendering the lubricatingcomposition corrosive, especially to alloy bearing metals containing acharacterizing proportion of cadmium, nickel, copper, lead, silver ortin and evento inhibit such corrosion by the lubricating oil base.

means hereinafter fully described and particularly pointed out in theclaims, the following description setting forth in detail certainapproved combinations of ingredients embodying my invention, suchdisclosed means constituting, however, but certain of various forms inwhich the principle of the invention may be used.

In general our invention comprises the addition of halogenatedthioethers to hydrocarbon lubricants to obtain the desired film strengthimprovement.

It is believed that under conditions of extreme pressure the halogenatedaddition agents of this invention reac-tchemically or physlcochemicallywith the metallic surfaces to form a non-fiuxing surface which will notseize or score. This invention is not intended to be limited, however,by any particular theoryor explanation of the action upon the metallicsurfaces.

All of the various halogens are effective when employed in accordancewith the present invention but chlorine is generally. preferred inasmuchas it is the least expensive and one of the most effective of thehalogens. Bromine and fluorine are more expensive and the latter isrelatively difiicult to handle but they are each usable in accordancewith this invention. Iodine is not so readily obtainable as the otherhalogens and is quite expensive but it also is satisfactory in providingeffective addition agents. It should also be noted that two or moredifferent halogens may be present in the same molecule. The brom-chlorand fiuorinated chlorine or bromine compounds give'especiallysatisfactory results.

Halogenation may continue until sumcient halogen to form the mono-chlorproduct has been added or'mixtures of less or greater halogen contentmay be employed. The halogen content of the halogenated thioether to beadded to the lubricant may vary from about 5% to about The halogenatedthioethers contemplated for use in accordance with our invention will befound to be particularly useful in that they combine the desirablecharacteristics of both sulphur and halogen in a single addition agentandv in such form that a cooperative result; not secured by any othertype of addition agent, is attained. The outstanding characteristic ofthe halogenated thioethers which makes them particularly suitable asaddition agents is their provision of generally higher film strength dueto the combined presence of both sulphur and halogen in the oil, coupledwith their corrosion inhibitor effect-on the surfaces being lubricated.Unusually high film strength combined with effectiveness'as a corrosioninhibitor is a characteristic not usually possessed by film strengthaddition agents. Specific examples of the halogenated thioethers whichmay be employed in attaining the above-named desirable ends are asfollows:

- (A) Chlorinated aliphatic thioethers:

(1) Diohloro-di-ethyl sulfide (2) Chlorodi-n-butyl sulfide (3)Chlorodilauryl sulfide (4) Chloro-ethyl octadecyl sulfide (5) Chlorooctadecyl butyl sulfide ethers:

p-Chloro-o-cresyl ethyl sulfide Chloroethyl' phenyl sulfide4-chloronaphthyl lauryl sulfide (4) p-Nitro-o-chloro phenyl octadecylsulfide (5) 2-hydroxynaphthyl-fl-chloroethyl sulfide (D) Chlorinatedalicyclic thio-ethers:

(1) Monochloro cyclohexyl sulfide (2) Dichioro cyclohexyl sulfide (3)Tetrachloro cyclohexyl sulfide (4) Chloro cyclopentyl sulfide (5) Chlorocyclobutylsulfide (6) .Chloro methyl cyclohexyl sulfide (7) Sym-dichlordipentyl cyclohexyl sulfide (8) Sym-dichlor dioctadecyl cyclohexylsulfide (9) Chlor cyclohexyl phhyl thio-ether (10) Chloro cyclonexylbenzyl thio-ether (E) Chlorinated heterocyclic thio-ethers:

(1) Chloro furfuryl thio-ether (2) Chloro iurfuryl methyl thio-ether (3)Chloro furfuryl phenyl thio-ether (4) Chloro furfuryl cyclo hexylthio-ether vention to provide the addition agents in the form of aconcentrate in a suitable oil, said 011 containing rather highpercentages of the addition agents. Such concentrates may be employedfor future blending with alubricating oil in the proportions desired forthe particular conditions of use.

When used in conjunction with a mineral lubricating oil it is obviousthat generally only such amounts of the addition agent may be includedas are soluble in the specified amount of oil. By the term soluble" asherein used it is intended to indicate the ability to form not only truesolutions but also any form of substantially permanently homogeneouscomposition when incorporated in mineral oil. With most of the compoundsthere is usually little difliculty, especially if the incorporation iseffected in the manner described in Cornell Patent No. 2,042,880,

and since quite small percentages often give remarkably improved resultsit is seldom of extre'me importance that the addition agents beoil-soluble in all proportions.

The halogenated thioethers are quite eflfective when used in relativelysmall amounts as addition agents to lubricating compositions. Thisinvention contemplates the use of from about 0.1% or even less to about20% by weight, based on the amount of oil, of these addition agents andfor the crankcase of internal combustion engines amounts from about 0.1%to about 2% are often suflicient. In the case of gear lubricants largerquantities, from about 2% to about 10%, may often be preferred. 1However, under certain relatively unusual circumstances where thethickfilm and other properties of the ordinary mineral lubricating oilare not required to any great de- (0) Chlorinated mixedaromatic-aliphatic thiogree the addition agent of this invention may beemployed as the major component of the lubrieating composition, onlysuch proportion of lu-' bricating oil being present as may be requiredto afiord the characteristics desired.

Since,' in general, the loss of the addition agent by volatilizationwill be less for compounds having a low volatility, the vapor pressureof the compounds should, for most purposes, be less than atmosphericpressure at temperatures up to 140 C. It is often desirable, especiallyfor use in internal combustion engines, that the vapor pressure be lessthan atmospheric at temperatures up to 170 C. In the case of compoundswhich are stable at temperatures up to their boiling points, thiscondition may be expressed by stating that the boiling point'of thecompound should, in general, be higher than 140 C., and for certainuses, such as internal combustion engines, higher than 170 C.

While the lubricating compositions which have been described herein asillustratin one embodiment of the invention have been generally referredto as oils, 1. e., liquids, this invention is, however, also applicableto the solid and semisolid types of lubricants commonly referred to inthe trade as greases, bodied oils, etc.

The compounds of this invention are highly eflective when employed asaddition agents to lubricants for internal combustion engines such asairplane and Diesel engines. The halogenated thioethers are especiallydesirable for such uses inasmuch as both sulphur and halogen are foundincluded in the same molecule thus affording a very effectivecomposition which is nevertheless safe and non-corrosive under diificultoperating conditions.

While mineral oil generally is the principal ingredient of thelubricating composition, it is not essential that it be the onlyingredient other than the addition agent, provided that there be noadditional ingredient which is incompatible with such addition agent. Itis within the contemplation of this invention to include, if necessaryor desirable, such other addition agents as are commonly added toimprove the viscosity index or cold test of the lubricant and alubricating composition according to this invention which also has aseparate oiliness-increasing agent has been found to be especiallyeffective.

Other modes of applying the principle of our invention may be employedinstead of the one explained, change being made as regards thecomposition and method herein disclosed, provided the ingredients orsteps stated by any .of the following claims or the equivalent of suchstated ingredients or steps be employed.

We, therefore, particularly point out and distinctly claim as ourinvention:

1. A lubricating composition comprising a major proportion of mineraloil and a halogenated thio-ether.

2. A lubricant comprising in combination a major proportion of an oil oflubricating viscosity and a halogenated thio ether.

3. A lubricating composition comprising a major proportion of mineraloil and a minor amount of a halogenated thio-ether.

4. A lubricating composition 0 mprising a major proportion of mineraloil a from about cm. to about 20%, by weight based on the to about 10%,by weight, based on the amount oi mineral oil, oi a halogenatedthin-ether.

6. A lubricating composition comprising a major proportion of mineraloil and irom about 0.1% to about 2%, by weight, based on the amount oimineral oil, oi a halogenated thio-ether.

7. A lubricating composition comprising a major proportion oi mineraloil and a minor amount oi a halogenated thio-ether having a vaporpressure less than atmospheric at 140 C.

8. A lubricating composition comprising a major proportion oi mineraloil and irom about 0.1% to about 20%, by weight, based on the amount oimineral oil, oi a halogenated thio-ether having a vapor pressure lessthan atmospheric at 140 C.

9. A lubricating composition comprising a major proportion oi mineraloil and irom about 0.1% to about 10%, by weight, based on the amount ormineral oil, oi a halogenated thio-ether, havinga vapor pressure lessthan atmospheric at 140 C.

10. A lubricating composition comprising a ma- :Ior proportion oimineral oil and from about 0.1%

to about 2%, by weight, based on the amount oi mineral oil. of ahalogenated thio-ether having a vapor pressure less than atmospheric at140 C.

11. A lubricating composition comprising a major proportion oi mineraloil and a minor amount oi a halogenated thio-ether having a vaporpressure less than atmospheric at 1'70 C. p 12. A lubricatingcomposition comprising a maior proportion oi mineral oil and irom about0.1

to about 20%, by weight, based on the amount oi mineral oil,- oi ahalogenated aliphatic thin-ether havirog a vapor pressure less thanatmospheric at 1 C. J

ummmmr de m 13. A lubricating composition comprising a major proportionoi mineral oil and irom about 0.1% to about 20%, by weight, based on theamount oi mineral oil, oi a halogenated aromatic thio-ether lligving avapor pressure less than atmospheric at 14. A lubricating compositioncomprising a major proportion oi mineral oil and from about 0.1%. toabout 20%, by weight, based on the amount of mineral oil, oi ahalogenated alicyclic thio-ether llizg'ing a vapor pressure less thanatmospheric at C.

15. A lubricating composition comprising a ma- Jor proportion oi mineraloil and irom about 0.1% to about 20%, by weight, based on the amount oimineral oil, oi a halogenated cyclic this-ether having a vapor pressureless than atmospheric at 140 C.

16. A lubricating composition comprising a ma-' ior proportion oimineral oil and irom about 4% to about 20%, byweight, based on theamount oi mineral oil, oi a-halogenated cyclo-aliphatic thio- BERT H.LINCOLN. JOHN W. WOLFE,

V non of the. Estate of Alfred Hem-Ibsen, Deceased.

